Detergent



Patented May 19, 1942 DETERGENT Lawrence H. Flett, Hamburg, N. Y.,assignor to Allied Chemical & Dye Corporation,

tion of New York a corpora- No Drawing. Application July so, 1936,Serial No. 93,521

27 Claims.

This invention relates to improvements in a1- kyl aromatic sulfon'atesuseful as detergent, wettin penetrating, emulsifying and like agents,and the manufacture thereof. It relates particularly to improvements inalkyl aromatic sulfonate detergents and their manufacture for use inwashing, laundering, scouring, cleaning and like processes of removingdirt, grease, etc. from materials of variouskinds, as well as for -useas toilet preparations.

In my copending application Serial No. 737,777, filed July 31, 1934, ofwhich the present application is a continuation-in-part and which is acontinuation-in-part of my co-pending application Serial Nos. 691,081and 691,082, filed September 26, 1933, I have disclosed the productionof mixtures of sulfonated products of the type AHRS obtained frompetroleum distillates (A representing an aromatic nucleus which maycontain substituents, H representing a nuclear hydroxyl group, Rrepresenting a nuclear alkyl group containing not less than 7 carbonatoms, and s representing a nuclear sulfonic acid group which may be inthe form of a free acid or a salt thereof).

According to the present invention, detergent, wetting, emulsifying andrelated compositions comprising mixtures of aromatic sulfonatescontaining higher alkyl groups as substituents, in which said higheralkyl groups are derived from aliphatic hydrocarbon mixtures of arestricted boiling range, are obtainable by processes com prisinghalogenation of an aliphatic hydrocarbon mixture of restricted boilingrange, condensation of the resulting halogenated products or selectedfractions thereof with an aromatic compound, and sulfonation of theresulting products or selected fractions thereof. Generally thesulfonated products are converted to their corresponding salts for use.

I have found, according to the present invention, that mixtures ofaliphatic hydrocarbons of a boiling range restricted to correspond withmixtures of hydrocarbons of which at least 80 per cent have an empiricalcarbon content (based on the boiling points of the hydrocarbons) notless than 12 and not more than 19 carbon atoms per molecule, constitutea valuaable source of aliphatic radicals'for the production of the mixedalkyl aromatic sulfonates. I have found furthermore, according to thepresent invention, that mixtures of alkyl aromatic sulfonates in whichthe alkyl groups are derived from aliphatic hydrocarbons of the saidboiling range are particularly valuable as detergent compositions, beingmuch superior to soaps derived from higher fatty acids in many respects.Thus, I have found, by chlorinating a petroleum distillate, such as akerosene fraction of Pennsylvania petroleum, of which at least 80 percent boils over a maximum range of 55 0. between the limits 210 and 320C., condensing the chlorination product with an aromatic compound, andsulfonating the resulting condensation product, compositions areobtained which, in the form of the free sulfonic acids or their salts(especially the latter), are useful for detergent, cleansing, wettingand other purposes. (Boiling temperatures referred to herein are atatmospheric pressure unless otherwise stated.) The method of determiningthe boiling ranges for the purposes of this invention is that describedby Weiss in Journal of Industrial 8; Engineering Chemistry, vol. 10(1918), pp. 1006-1008.

The alkyl aromatic sulfonates of the present invention have theadvantageous properties of being excellent washing agents which are veryeffective under widely different conditions, for example, in baths ofhard or soft water; under acid, neutral, or alkaline conditions; in thepresence or absence of water insoluble solvents; and in concentrated orvery dilute solutions.

As is well known in the art, petroleum distillates are mainly mixturesof aliphatic hydrocarbons, including both saturated acyclic aliphatichydrocarbons containing straight or branched carbon chains and cyclicaliphatic hydrocarbons, as well as some unsaturated aliphatichydrocarbons, depending upon the source of the petroleum and the methodof distillation and/or purification. When the petroleum distillates arehalogenated in the preparation of products of the present invention,mixtures of various halogenated derivatives of the said allphatichydrocarbons are produced (which are generically referred to herein asalkyl halides), and the said mixtures of alkyl halides, when condensedwith aromatic compounds, produce mixtures of alkyl aromatic compounds,in which the alkyl groups correspond with aliphatic hydrocarbons of thepetroleum distillate from which they were produced. Accordingly, whenthe mixtures of alkyl aromatic compounds are sulfonated, compositionsare produced which contain mixtures of sulfonated allq'l aromaticcompounds duffering from each other in the alkyl groups, which groupscorrespond with the aliphatic hydrocarbons of the mixture employed.

The present invention thus has the additional advantage that it providesa relatively simple and direct method of producing products havingvaluable detergent and other properties from raw material which isreadily available in large quantities; thereby making feasible theeconomical production of such products on a commercial scale. I

320" C. Distillates of this type are believed to contain aliphatichydrocarbons of which at least 80 per cent contain between 12 and 19oarbo atoms per molecule. I

Without limiting the invention to any theoretical explanations, itappears that the presence of mixtures of related alkyl aryl sulfonatesenhances the solubility and the detergent and wetting action of theproducts, while the restriction of the boiling range and quality of thealiphatic hydrocarbon mixtures employed results in greater uniformity inthe degree of chlorination among the respective hydrocarbons and hencein improved quality of the sulfonated products, with resultant improveddetergent action.

The aliphatic hydrocarbon mixtures preferably employed vary somewhatamong themselves, within the above limits, depending upon the type ofalkyl aromatic compound into which they are converted. Thus, for theproduction of mixed alkyl aromatic sulfonates derived from aromaticcompounds of the benzene series containing a solubilizing group inaddition to the sulfo group (as in the case, for example, of phenol,cresol, etc., derivatives), a hydrocarbon mixture of the above type ispreferably employed of which at least 80 per cent boils over a maximumrange of 55 C. (and preferably a maximum range of 30 C.) and between 235and 320 0., which boiling point limits are believed to correspond withhydrocarbons containing mainly 14 to 19 carbon atoms 'per molecule;whereas, for the production of mixed alkyl aromatic sulfonates derivedfrom aromatic compounds of the benzene series free from a solubilizinggroup other than the sulfo group, a hydrocarbon mixture of the abovetype is preferably employed of which at least 80 per cent boils over amaximum range of 55 C. (and preferably a maximum range of 30 C.) andbetween 210 and 265 C., which boiling point limits are believed tocorrespond with hydrocarbons containing mainly 12 to 16 carbon atoms permolecule.

The boiling point range of the hydrocarbon mixtures employed may varywith respect to the boiling point limits thereof: provided at least 80per cent thereof, and preferably at least a middle 80 per cent thereof,has the boiling characteristics above referred to. Thus, hydrocarbonmaterial oi which the first l per cent boils considerably below thepreferred lower limit and/or the last per cent boils considerably abovethe preferred upper limit may be employed in accordance with the presentinvention, if it has the characteristics herein referred to.

The preferred hydrocarbon mixtures employed in accordance with thepresent invention are exemplified by fractions of Pennsylvania andMichigan (Mount Pleasant) petroleum dlstillates in .the.ranges'mentioned above, and especially those whose boiling point limitsare 210 and 290 0.. These distillates consist essentially of open chainaliphatic (parafllnic) hydrocarbons a large portion of which areprobably relatively long carbon chains rather than more condensedmolecules. Such distillates will be referred to as of the Pennsylvaniatype, whether derived from natural sources or derived by processing orby purification of less favorable distillates from other sources.

The alkyl 'aromatic sulfonates of the present invention may bederivatives of various aromatic hydrocarbons, as for example, benzene,toluene, xylene, diphenyl, naphthalene, anthracene, etc. They maycontain one or more substituents in the aromatic nucleus, in addition tothe alkyl group derived fromthe said hydrocarbon, of which the followingare illustrative: '-0H; OX, where X is an alkyl or aralkyl groupcontaining one to eight carbon atoms; COOMe, where Me is an alkalimetal, ammonium or water-soluble organic basic cation; -COO alkyl; NO2;-NHz; -NH alkyl; or

. alkyl I The products derived from aromatic compounds ofthe benzeneseries are preferred. Further, the products in which the alkylhydrocarbon radicals, derived from the aliphatic hydrocarbons abovereferred to, are attached to carbon atoms of the aromatic nucleus arepreferred.-

The said alkyl aromatic sulfonates may be in the form of the freesulfonic acid or in the form of a salt; for example, a salt resultingeither from thereplacement of the hydrogen of said sulfonic acid groupwith its equivalent of a metal (preferably an alkali metal) or from theaddition of ammonia or an organic base.

In preparing the sulfonated products in accordance with one preferredmethod of procedure, an aliphatic hydrocarbon distillate of thecharacter described above is chlorinated or otherwise halogenated, forexample, in accord ance with known processes for the production ofchlorinated or other halogenated derivatives of aliphatic hydrocarbons,whereby mixtures comprising chlorinated or other halogenated aliphatichydrocarbons are produced; an aromatic hydrocarbon, or derivative,adapted to provide the desired aryl radical of the product is thenconverted to a mixture of alkyl aromatic compounds by a processincluding reaction of the aromatic compound with the mixed chlorinatedor other halogenated aliphatic hydrocarbons, or with a selected portionthereof; and the resulting mixture of alkyl aromatic compounds, or aselected portion thereof, is then sulfonated with or without previousconversion to further derivatives thereof. The resulting mixture ofsulfonic acids is preferably converted into a mixture of theircorresponding salts. If inorganic salts are simultaneously formed, theymay be left in the mixture of said sulfonic acid salts, or they may beseparated therefrom, as the use of the product may determine.

The invention will be illustrated by the following specific examples. Itwill be realized by those skilled in the art that the invention is notlimited thereto, except as indicated in the appended patent claims. Theparts are by weight, the temperatures are in degrees centigrade and thepressure is atmospheric pressure, unless otherwise indicated.

Emample 1.-A Pennsylvania petroleum distillate (kerosene) which distillsfrom about 200 to aaeaioo about 266. and of which about 80 per centdistills over the range of about 220 to 260, and which comprisessubstantially a mixture of'hydrocarbons which are chiefly aliphatic andsaturated, is chlorinated at about 50 by passing through it a stream ofchlorine gas until the chlorinated mixture has increased in weight byabout 20 per cent because of organically-combined chlorine therein. Theresulting mixture of unchlorinated and chlorinated hydrocarbons isaerated to remove practically all dissolved hydrogen chloride. Thechlorinated hydrocarbons in the mixture contain a preponderant amount ofmonochlor hydrocarbons.

Example 2.-Chlorine is passed into a kerosene (a purified Pennsylvaniapetroleum distillate) boiling from 245 to 315, and of which 90 per centdistills between 260 and 305, and having a specific gravity of 0.815,contained in a closed, lead-lined assel which is equipped with a ventfor hydrogen chloride produced by the chlorination. The chlorination iscarried out in the dark, but to facilitate the chlorination the keroseneinitially contains about 0.45 part of iodine per 1000 parts of kerosene.The temperature of the reaction mass is preferably maintained at about45 to 50. The introduction of chlorine is continued until the weight ofthe mass increases to an extent corresponding substantially with 115 percent of the theoretical amount for the formation of the monochloride.The specific gravity of the reaction mixture reaches about 0.915.

Example 3.Pennsylvania kerosene is frac tionated and 300 parts of thedistillate therefrom boiling from about 240 to 260 is chlorinated in asuitable reactor by passing chlorine gas slowly into the distillate at atemperature of about 55 until its weight has increased, because oforganically combined chlorine, to 353 parts. Dissolved hydrogen chlorideis reduced to about 1.2 parts by aeration.

The chlorinated distillate is substantially a mixture of chlorinated'and unchlorinated open chain saturated hydrocarbons which have anaverage molecular carbon content of about 14 carbon atoms. Thechlorinated hydrocarbons in the mixture comprise about equal amounts ofmono and polychlorinated hydrocarbons. By distillation, the mixture canbe separated into three fractions which respectively containsubstantially the unchlorinated, monochlorinated and polychlorinatedhydrocarbons.

Example 4.A Pennsylvania petroleum distillate, 90 per cent of whichdistills from about 265 to about 303 is selected as a mixture whichcontains a preponderating amount of open-chain saturated hydrocarbonswhich have an average carbon content of 16 to 17 carbon atoms permolecule. In a suitable reactor, 623 parts of such a distillate arechlorinated by passing a stream of chlorine gas through the saiddistillate while it is exposed to difiused sunlight and maintained atabout 60. Chlorination is continued until the distillate has increasedin weight to about 729 parts because of organically-combined chlorinetherein. Dissolved hydrogen chloride in the chlorinated mixture isreduced to about 2 parts (0.3 per cent HCl) by aeration for aboutminutes. The increase is approximately 115 per cent of the theoreticalincrease required for monochlorination of the hydrocarbons in thedistillate.

The chlorinated distillate is chiefly a mixture of unchlorinated andchlorinated open chain saturated hydrocarbons with from about 16 toabout 17 carbon atoms in their molecules. The predominating chlorinatedhydrocarbons in the mixture are the monochlor hydrocarbons.

Example 5.--Part 1: 30 parts of anhydrous aluminum chloride are addedslowly to an agitated mixture of 200 parts of benzol and 300 parts ofamixture containing chlorinated and unchlorinated hydrocarbons andprepared as described in Example 1. The mixture is cooled externallyuntil the vigorous evolution of hydrogen chloride gases from the mixturehas abated. It is then heated and maintained at its refluxingtemperature for about one hour, or until the evolution of hydrogenchloride has ceased. The reacting mass is cooled and drowned with amixture of about 400 parts of crushed ice, 200 parts of water and 50parts 'of commercial muriatic acid. The mixture is allowed to stratify,the organic oily layer above the aqueous solution-is separated, washedwith a small amount of water, and distilled. The portion which distillsfrom about 160 to about 210 at 4 mm. of mercury pressure is collectedand consists of a mixture of alkylated benzenes in which the alkylgroups predominantly contain from about 12 to about 15 carbon atoms. Theresulting mixture is a light amber-colored, somewhat oily, but notviscous, liquid which is insoluble in water, but soluble in the commonorganic solvents.

Part 2: parts of the distilled oil obtained according to Part 1 of thisexample are mixed with parts of 20 percent oleum at a temperature ofapproximately 10. The mixture is allowed to warm to 25 to 30 and isstirred at this temperature for 1 to 3 hours or until one part of a testportion, after neutralizing with sodium hydroxide, is soluble in 20parts of water. The mixture is then poured into approximately 600 partsof an ice-water mixture, and the resulting solution is made neutral toBrilliant Yellow and Congo red papers with caustic alkali (e. g., sodiumhydroxide). The neutralized solution is evaporated to dryness on arotary drum drier. The product obtained is in the form of light-buff towhite flakes. It comprises chiefly a mixture of alkyl benzene sulfonatesand alkali metal sulfate. Aqueous solutions of the product haveexcellent washing properties, as well as good wetting, insecticidal, andfungicidal properties.

Example 6. -Part 1: 150 parts of a crude chlorinated kerosene mixture ofthe type produced in the above Examples 1 to 4, 90 parts of naphthalene,and 25 parts of anhydrous zinc chloride are thoroughly mixed byagitation and heated to about in a reactor fitted with a refluxcondenser. The mixture is kept at about 135 for about 45 minutes oruntil the evolution of hydrogen chloride has practically ceased. Thereaction mixture is cooled, mixed with water, allowed to settle and theupper (organic) layer is withdrawn and washed with water until it isreasonably free from water-soluble products. The washed organic liquidmass is distilled in vacuo, and the fraction which distills between and250 at 8 to 12 mm. of mercury pressure is collected as a yellowishliquid.

Part 2: 100 parts of the distilled oil obtained according to Part 1 ofthis example are treated, with good stirring, at 10 with 120 parts of 7per cent oleum. The mixture, while being stirred, is then allowed towarm up to 25 to 30, and that temperature is maintained for 1 to 2 hoursor until a neutralized test portion is soluble in twenty times itsweight of water. The sulfonation mixture is then drowned in three timesits Weight of an ice-water mixture. The resulting solution 'isneutralized with caustic soda and evaporated to dryness, as in Example5, Part 2. The product is in the form of light-buff to white flakes. Itcomprises chiefly a mixture of sulfonates of alkyl naphthalenes andalkali metal sulfate. Its aqueous solutions have good wetting, washing,and parasiticidal properties.

Example 7.-Part 1: 300 parts of a chlorinated kerosene mixture of thetype produced in the above Examples 1 to 4 is mixed with 30 parts ofanhydrous aluminum chloride and 150 parts of commercial diphenyl. Themixture is agitated under reflux at room temperature (that is, at about15 to 30) for about one hour and thereafter at about 75 for about oneand a half hours. The mass is then cooled to about 20 to 30 and pouredinto a mixture of 600 parts of ice water and 30 parts of commercial'muriatic acid. The aluminum salts dissolve in the cold dilute acidwhile the organic matter which contains the alkylated diphenyl compoundsis precipitated in a semi-liquid, pasty form. Small amounts of benzeneand/or ether are added to the agitated aqueous mixture to dissolve theorganic products. Upon standing, the mixture separates into an upperlayer which is a solution of the organic matter in the organic solvent,and a lower aqueous acid layer which is withdrawn and discarded. Thebenzol and/or ether solution of organic matter is washed with wateruntil it is reasonably free of acid, and is then distilled in vacuo. Thefraction of the distillate which boils at about 170 to about 260 at 5mm. pressure is collected separately. It isa light-yellow viscous oilwhich is insoluble in water, but soluble in benzene and in ether. It isa mixture comprised chiefly of alkylated diphenyl compounds in which thealkyl groups correspond with the kerosene hydrocarbons employed. It mayalso contain some chlor-alkyl diphenyl compounds derived from thedichlor hydrocarbons.

Part 2: 25 parts of the oil obtained according.

to Part 1 of this example are mixed with parts of 100 per cent sulfuricacid and stirred at about 90 for about minutes, or until a 1 cc. sampleis practically completely soluble in about 10 ccs. of water at about Thesulfonation mass is poured into 300 parts of water and the aqueous acidmixture is neutralized with caustic alkali or a water-soluble carbonate(e. g., sodium carbonate), and the resulting neutral solution is dried.The product is chiefly a mixture of the salts (e. g., alkali metalsalts) of alkyl-diphenyl sulfonic acids. It is a light-brown to whitesolid which is soluble in water, and in aqueous solutions of mineralacids and of water-soluble alkalies.

Example 8.560 parts of the mixture of chlorinated hydrocarbons producedin Example 2, 350 parts of phenol and 28 parts of granular anhydrouszinc chloride are agitated at room temperature for about 3 hours andthen heated, with agitation, at about 135 for about 5 hours. Theresulting reaction mass is cooled and added to about 600 parts of water,the mixture is heated to 70 with agitation, allowed to settle, and theupper, oil layer is separated and washed with hot water to remove zincchloride and residual phenol. The washed oil is then treated with asmall amount of alkali ('7 parts of a 50 per cent solution of sodiumhydroxide) and distilled in vacuo (e. g., 4 mm. pressure) in a stillequipped with a fractionating column. Fractions boiling between about140 and 230 at 4 mm. pressure are collected as separate products or asone prodnot.

262 parts of one of the resulting mixtures of alkyl phenols (theresulting product or one of the fractions thereof) are sulfonated byagitating well with 262 parts of 100 percent sulfuric acid, whilemaintaining the temperature at 20 to 30. When the sulfonation has beeneffected, the reaction mass is drowned in 1500 parts of water, treatedwith sufiicient caustic soda to render it neutral to Delta paper (about260 parts of a 50 per cent solution of caustic soda), and evaporated todryness.

If desired, the crude non-fractionated product which boils above 140 maybe sulfonated instead of the fractionated product or products. Theresulting sulfonated product is generally somewhat darker in color.

Example 9.Part 1: Chlorine is passed into 400 parts of a keroseneboiling from about 195 to about 300 (over 80 percent of which boils fromabout 225 to 275), having a specific gravity of 0.799 at 24, containingabout 5.6 per cent of unsaturated hydrocarbons, and having a probablecarbon content ranging mainly from 13 to 16 carbon atoms per molecule,at 50 in diffused sun-light until there is an increase of weight of 111parts, 2 parts of which is due to dissolved hydrogen chloride. Theresulting product comprises unchlorinated hydrocarbon in admixture withmono-, di-, and poly-chlorinated hydrocarbons, the average chlorinecontent of the mixture being equivalent to about one and one-half atomsof chlorine per molecule ofhydrocarbon having the stated carbon content.

Part 2: 150 parts of the chlorinated mixture produced in Part 1 of thisexample is slowly added to an agitated mixture of 200 parts of phenoland 5 parts of anhydrous zinc chloride at and the temperature ismaintained at 75 for about 30 minutes after all the chlorinated mixturehas been added. The temperature of the mixture is then raised andmaintained at for 2.5 hours. 5 parts of Zinc dust is then added, andafter one hour another 5 parts of zinc dust is added, the temperaturebeing maintained during this addition, and for about 3 hours afterward,at 135. The reaction mixture is cooled, treated with water, and the oilis separated from the water and residual zinc dust and fractionallydistilled. The fraction boiling from to 250" at 4 mm. pressure isseparately collected. The product, which is an oil showing fluorescenceunder ultra-violet light, insoluble in water, soluble in alcohol,gasoline, and other organic solvents, is comprised mainly of a mixtureof alkyl phenols which may be represented by the general formula:

drocarbon mixture is prepared by chlorinating at 50, in a lead-linedvessel, a kerosene of the type employed in Example 9, until the reactionmixture reaches a specific gravity or 0.91.,

Part 2: 150 parts of the product of Part 1 of this pie is reacted with200 parts of phenol as described in Example 9. The crude alkyl phenolproduct is washed with water and distilled in vacuo. Thefractiondistilling-trom 140 to 240? at 3 mm. pressure isseparatelycollected. It comprises a mixture or alhl phenols in which the alkylgroups correspond with. the hydrocarbons oi the kerosene, being probablyfor the main part saturated alkyl hydrocarbon groups.

Part 3: The crude oil obtained in Part 2 of this example is fractionallydistilled in vacuo and the distillate boiling from 175 to 225 at 4 mm.pressure is separately collected. To 25 parts of this distillate, underagitation and maintained at a temperature of 30, there is slowly added11.6 parts of chlorsulfonic acid. The mixture is agitated for 15 minutesafter-all of the chlorsulfonic acid has been added, The temperature ofthe mixture is then raisedand held at 70 for 15 minutes. The mixture isthen drowned in 250 parts of water, the solution is made neutral tobrilliant yellow and Congo red papers by addition of caustic sodathereto, and evaporated to dryness on a double drum drier. The resultingproduct comprises the sodium salts of a mixture of alkyl phenol sulfonicacids in which the alkyl groups are mainly saturated aliphatichydrocarbons. It is a light colored to white powder substantially iree(less than 4 per cent) of inorganic salts.

Example 11 .--1O parts of the alkyl phenol mixture obtained in Example10, Part 2, are stirred and thereto 10 parts of sulfuric acidmonohydrate (100 per cent sulfuric acid) are added slowly so that thetemperature of the reaction mixture does not exceed about 30 to 35. Thesulionation mixture is then warmed to-40 and held at that temperatureuntil a sample is completely soluble in neutral, acid and alkalinewater, and/or does not precipitate calcium salts from a calcium chloridesolution containing the equivalent of 0.224 gram calcium oxide per liter(30 to 90 minutes). The solution is sometimes slightly turbid due to thepresence of insoluble impurities. The sulfonation mass is then dilutedwith water to about 100 parts by weight and neutralized with sodium orpotassium hydroxide, or their equivalents. The neutral solution ofsulfonates is filtered and evaporated to dryness.

The final product is a mixture of sodium (or potassium, etc.) salts ofalkyl phenol sulfonic acids which in the free state correspond with thegeneral formula in which R is a primary, secondary or tertiaryalkylgroup. The alkyl group is probably para, and the sulfonic acidgroup is probably ortho to the hydroxyl group. i

Example 12-150 parts of the crude, undis-. tilled chlorinatedhydrocarbon product prepared in Example 10, Part 1, 150 parts of phenol,130 parts 01' anhydrouszinc chloride and 10 parts oi tetrachlorethaneare heated under refluxing and agitation at 140 to 150 for about 3%hours, an additional 10 parts of .tetrachlorethane being added after thereaction has proceeded forabout 2 hours. The oily reaction mixture isdecanted aaeaico from the zinc chloride, washed with per centhydrochloric acid and fractionally distilled in vacuo. The portion orthe distillate boiling from V 180f'to 240 at 10 mm. pressure isseparately collected. It is similar to the product resulting from theprocess of Example 10, Part 1, and can be similarly sulfonated toproduce a similar sulionated product.

Example 13.Part 1: Chlorine is passed into 300. parts of kerosene(boiling from about 210 to about 255, and for the most part from about220 to 240) at 5 to 15until there is a gain in weight of 58 parts,exclusive of the smallamount of dissolved hydrogen chloride present.

Part 2: 150 parts of the resulting chlorinated kerosene, 70 parts ofcommercial cresylic acid, and 25 parts of anhydrous zinc chloride areagitated vigorously and heated at 135 for 45 minutes. After cooling, theliquid is decanted from the solid material and washed with about 100parts of 10 per cent hydrochloric acid. The washed oil is vacuumdistilled, and the fraction of the distillate boiling between 190 and240 at 8 mm. pressure is separately collected. It is an amber to whiteliquid and is comprised chiefly of a mixture 01' alkyl cresolscorresponding with the general formula:

CHi

1 in which R' is a primary, secondary or tertiary alkyl group.

Part 3: 100 parts of the mixture of alkylated cresols as prepared inPart 2 of this example are agitated rapidly while 128 parts of sulfuricacid monohydrate (100 per cent sulfuric acid) are added with temperatureof the sulfonation mixture controlled to remain around 30 throughout theaddition. The sulfonation mass is then warmed to and held there until a.sample is completely soluble in water and/or does not precipitatecalcium salts (about 30 minutes). The sulfonation mass is then diluted,neutralized with caustic soda, filtered and evaporated to dryness. Theresulting product is a mixture of alkyl cresol sulfonates.

Example 14. parts of the crude chlorinated hydrocarbon product preparedin Example 9, Part 1, 100 parts of p-cresol and 80 parts of anhydrouszinc chloride are agitated while being heated at in a vessel providedwith a reflux condenser. After about 4 hours the heating is discontinuedand the mixture is allowed to cool. The oily product is decanted fromthe zinc chloride, washed with dilute hydrochloric acid and fractionallydistilled in vacuo. The portion of the distillate boiling from to 210 at7 mm. pressure is separately collected. It comprises mainly a mixture ofalkyl p-cresols which may be represented by the general formula:

atoms in the alkyl groups represented by 3''" probably being mainly from13 to 16.

Example 15.100 parts of o-cresol or mcresol are employed instead of thep-cresol of Example 14. The portion of the resulting mcresol productboiling from 185 to 205 at 6 mm. pressure, and the portion of theo-cresol product boiling from 160 to 250 at 4 mm. pressure, areseparately collected. They respectively comprise mainly a mixture ofalkyl m-cresols and alkyl o-cresols, and can be sulfonated in the mannerherein described to produce corresponding alkyl cresol sulfonates.

Example 16.-P art 1: 150 parts of the chlorinated kerosene of Example13, Part 1, 80 parts of 'o-chlorophenol and 40 parts of anhydrous zincchloride are agitated vigorously and heated at 135 for 45 minutes. Theliquid is decanted from the solid and washed once with about 100 partsof per cent hydrochloric acid. The oil is vacuum distilled. The fractionboiling between 180 and 250 at 8 mm. pressure is collected separately.It is a brown to white liquid comprised-chiefly of a mixture of alkylo-chlorophenols corresponding with the general formula in which R hasthe meaning above given in Example 9. 4

Part 2: The mixture of alkylated o-chlorophenols obtained in Part 1 ofthis example is sulfonated and isolated in the manner described inExample 13, Part 2. The resulting product comprises a mixture of alkylchlorophenol sulfonates having properties similar to those of the otheralkyl phenol sulfonates herein described.

Example 17.150 parts of the chlorinated kerosene of Example 13, Part 1,90 parts of salicylic acid and 50 parts of anhydrous zinc chloride areagitated vigorously and heated at 140 to 150 for 4 hours. When thereaction mixture cools to 80, 100 parts of water are added, and thenabout 70 parts of ether. The zinc chloride is removed by washing severaltimes with water. The ether solution is extracted with sodium carbonatesolution. The sodium carbonate solution is boiled to remove anydissolved ether, acidified with hydrochloric acid and heated. The excesssalicylic acid dissolves and leaves the alkyl salicylic acid as an oil.The crude alkylated salicylic acid when cold is a brown, gummy solid. Itforms a good detergent with alkali.

Example 18.-Part 1: A chlorinated kerosene mixture of the type producedin Examples 1 to 4 is produced by fractionally distilling a crudechlorinated kerosene prepared as described in Example 1, from a kerosenecontaining mainly hydrocarbons having 13 to carbon atoms per molecule,and separately collecting the fraction boiling from 120 to 160 at 3 mm.pressure. 200 parts of this fraction are mixed with 150 parts of8-hydroxyquinoline, and to this mixture, with agitation, there areslowly and cautiously added 150 parts of anhydrous aluminum chloride. 50parts of tetrachlorethane are added, and the mixture carefully heated. Avigorous reaction develops which is controlled, if necessary, by coolingsame. After the reaction has moderated, the reaction mass is maintainedat a temperature of 90 for 3 hours, the mixture poured on to ice,acidified with hydrochloric acid, and the oil which separates is washedwith dilute caustic soda solution and distilled. The fraction whichdistills over at 200 to 230 at 3 mm. pressure is separately collected.The product thus obtained comprises a mixture of alkylatedhydroxyquinolines having the following general formula:

wherein R' is a primary, secondary or tertiary alkyl group, said alkylgroups containing mainly 13 to 15 carbon atoms.

Part 2: 10 parts of the mixture of alkyl hydroxy quinolines preparedaccording to Part 1 of this example are treated withparts of sulfuricacid monohydrate at 50 for 15 to 20 minutes, the reaction m'ass drownedin 300 parts of cold water, the solution is made neutral to Brom CresolGreen paper by addition thereto of caustic soda, and evaporated todryness. The resulting product comprises a mixture of the sodium saltsof the alkyl hydroxy quinoline sulfonic acids. It may be purified byextraction with alcohol, filtering, and evaporating the alcoholicsolution to dryness. The product has detergent and insecticidalproperties.

Example 19.-Part 1: A mixture of 300 parts of the chlorinatedhydrocarbon prepared in Example 10, Part 1, 200 partsparalwdroxydiphenyl and 35 parts of anhydrous zinc chloride is heatedunder a reflux condenser to refluxing temperature, with agitation, for 7hours. The mixture is cooled, a suflicient amount of ether and alcohol(equal parts) is added to dissolve the solid organic material which ispresent, and the alcoholether solution is washed with water anddistilled in vacuo. The portion boiling from 230 to 300 at 5 mm.pressure is separately collected. It is comprised of a mixture of alkylp-hydroxydiphenyls.

Part 2: To 25 parts of the mixture of alkyl p-hydroxydiphenyls preparedin Part 1 of this example there is slowly added 27 parts of sulfuricacid monohydrate. The mixture is agitated at for about 25 minutes,cooled, poured into water, and the aqueous solution is made neutral toBrom Cresol Green paper by addition of caustic soda thereto and thenevaporated to dryness. The resulting product comprises a mixture of thesodium salts of alkyl p-hydroxydiphenyl sulfonie acids in which thealkyl groups correspond with the hydrocarbons of the kerosene employed.

Example 20.-Part 1: A mixture of 200 parts of the chlorinatedhydrocarbon product prepared in Example 10, Part 1, 150 partsbeta-naphthol, and parts of anhydrous zinc chloride is stirred andheated to 180 for 5 hours. The reaction mass is cooled, extracted withether, and the ether extract is washed with water and then distilledunder reduced pressure. The product boiling from to 280 at 3 mm.pressure is separately collected. It comprises a mixture of alkylbeta-naphthols.

Part 2: 25 parts of the mixture of alkyl betanaphthols prepared asdescribed in Part 1 of this example are heated with 33 parts of sulfuricacid monohydrate at 95 for 2 hours. The resulting mass is drowned in 300parts of water, and the solution is made neutral to Brom Cresol Greenpaper by addition thereto of caustic soda. The neutralized solution'isdried on a double drum drier. The resulting product comprises a mixtureof alkyl beta-naphthol sulfonic acids in the form of the sodium salts.It is soluble in water, and has the properties of a detergent anddispersing agent.

Example 21.420 parts of bromine dissolved in 1600 parts of carbontetrachloride are slowly added in small portions at a time to 500 partsof a kerosene of the type employed in Examples 1 to 4 contained in a.glass vessel, at ordinary temperature in the presence of actinic lightfrom a mercury lamp. The resulting crude product, after distilling oilthe carbon tetrachloride, comprises a mixture of brominatedhydrocarbons. 108 parts of this crude product is mixed with 75 parts ofphenol and 10 parts of anhydrous zinc chloride, and the mixture isheated at 135 for 4 hours. The resulting mass is cooled, washed withwater, and distilled under reduced pressure. The fraction distillingbetween 140 and 205 at 4 mm. pressure is separately collected. Itcomprises a mixture of alkyl phenols similar to those produced with theaid of chlorine.

Example 22.Part 1: 200 parts of a crude chlorinated kerosene mixture ofthe type produced in the above Examples 1 to 4, 105 parts phenetol(boiling from 167to 172 at atmos pheric pressure) and 20 parts anhydrouszinc chloride are mixed in a suitable vessel fitted with a refluxcondenser and agitator. The agitated mixture is heated slowly to atemperature between 100 and 110, and maintained there for about 17hours. The reaction mixture is then cooled, the liquid portion isdecanted, mixed and washed with approximately 100 parts of a 10 per centaqueous solution of muriatic acid. The oil is separated from the aqueouslayer and distilled in vacuo. The portion of the distillate boiling from135 to 205 at 5 mm. (mercury) pressure is collected as a yellow, mobile,oil which is insoluble in water, dilute caustic soda and acid. It iscompletely and readily soluble in ethyl ether, benzene, carbontetrachloride, ethylene dichloride, etc. Its solubility in alcohol ismuch less than in the foregoing solvents. The oil is a mixture ofC-alkyl phenetols and some C-alkyl phenols, the major portion of themixture being the C-alkyl phenetols in which the nuclear substituentgroups are hydrocarbon residues which correspond with the hydrocarbonsfrom which the chlorinated kerosene is derived.

Part 2: 15 parts of the distilled mixture of alkylated phenetol of Part1 of this example are cooled to a temperature between and and while themixture is rapidly agitated, 28 parts of sulfuric acid monohydrate areadded slowly to it. During the acid addition the temperature of thesulfonation mass is maintained below 15. This mixture is agitated atroom temperature for about 1 hour until a sample is completely solublewhen neutralized with caustic soda in about 20 to 25 times the samplesweight of water. The mass is then diluted with about 100 parts of iceand water, carefully neutralized t0 faint alkalinity with aqueouscaustic soda, and the neutral solution is evaporated to dryness. Theproduct is chiefly a mixture containing the sodium sulfonates of mixedalkyl phenetols in which the alkyl groups are alkyl hydrocarbon radicalscorresponding with the alkyl chlorides from which they are derived. Theproduct is a pale-brown to white friable but granular solid which iseasily soluble in water and forms solutions which foam readily. Theproduct is soluble in alkaline, neutral or acid aqueous solutions madefrom hard or soft water, and does not precipitate any alkaline earthsalts from its solutions in hard water. characterized by their excellentemulsifying, dispersing, wetting and detergent powers.

The sodium sulfonates of the alkylated phenetols in the mixture can beextracted with alcohol in which they are soluble; and thereby freed frominorganic salts. They are also soluble'to an appreciable extent intoluene, benzene and naphtha.

Another and preferred method of making the alkylated aryl-alkyl ethersof this invention consists of two reactions. By means of the firstreaction a phenolic body is nuclearly alkylated to form a C-alkyl phenolmixture as described above; by means of the second reaction the hydroxylgroups of the C-alkyl phenols are etherified. The following exampleillustrates this method:

Example 23.Part 1: 75 parts of a mixture of nuclearly alkylated cresylicacids of the type produced in Example 13, Part 2, 50 parts of denaturedalcohol, and 23 parts of a 50% aqueous caustic soda solution are mixedin a vessel fitted with an agitator and a refluxcondenser. The mixtureis heated gently to its boiling point, and maintained at the temperatureat which the mixture refluxed gently throughout the subsequentetherification reaction. 40 parts of diethyl sulfate are added as acontinual but fine stream over a period of about 30 minutes. Refiuxingof the mixture is continued for about 1 to 1.5 hours after the last ofthe diethyl sulfate is added. The mixture is then cooled by addition ofabout 200 parts water, and after further agitation for about 30 minutesis filtered. The filtrate on standing separates by gravity, and theremaining upper layer of oil is distilled in vacuo. The fraction of thedistillate which distills between 140 at 3 mm. and 205 at 3 mm. iscollected separately and comprises a mixture of nuclearly alkylatedcresylic acid ethyl ethers. The mixture is a pale yellow, refractive,mobile oil which is insoluble in water or caustic soda. It dissolves inmost organic solvents, such as ethyl ether, carbon tetrachloride,ethylene dichloride and benzene. It is much less soluble in alcohol thanin the aforementioned solvents. The major portion of the material is amixture of C-alkyl cresyl ethers.

Part 2: 15 parts of the distilled mixture of nuclearly alkylated cresylethyl ethers of Part 1 of this example are agitated rapidly in asuitable vessel, cooled to about 0 and treated with small additions of 6parts of chlorsulfonic acid (about per cent to per cent of amounttheoretically required for monosulfonation). The temperature of thesulfonation mixture is not permitted to exceed 15 during the addition ofacid. The mixture is stirred for about 2 hours until a sample iscompletely soluble when neutralized with caustic soda in about 20 to 25times the samples weight of water. The sulfonation mass is then drownedin water, neutralized with caustic soda and evaporated to 'dryness.

The dry product comprises chiefly a mixture of sodium sulfonates ofC-alkyl cresyl ethyl ethers in which the alkyl groups correspond withthe alkyl halides of the chlorinated kerosene. It is a pale yellow,friable solid, which dissolves readily in water to a faintly yellowsolution having excellent detergent, wetting and dispersing properties.

The aqueous solutions are In a similar manner other mixtures ofalkylated alkoxy-aromatic compounds containing 1 to 8 carbon atoms inthe alkoxy radical (which may be an aralkoxy radical) can be producedfrom the corresponding alkoxy-aromatic compounds, or from the mixedalkyl hydroxy-aromatic compounds herein described and alkylating agentscontaining 1 to 8 carbon atoms in the alkyl group.

Example 24.Part 1: 42 parts of mixed acid which contains about 29 percent nitric acid and about 57 per cent sulfuric acid, are added veryslowly to 50 parts of the mixture of alkylated benzene preparedaccording to above Example 5, Part 1. The rapidly agitated mass ismaintained at a temperature below 30 throughout the period of additionof mixed acid, and for about 30 minutes after the addition is complete.The nitrated mass is then diluted with about an equal volume of waterand allowed to stand. The mixture of nitrated alkylated benzeneseparates as an oily upper layer which is removed from the lower layerof aqueous acid. It is washed with water until reasonably free of acid,then with a dilute solution of alkali and finally with water untilpractically neutral. The oil thus obtained has a light red to browncolor. It is a mixture of alkyl nitro benzenes, and most probablycontains only mononitro compounds.

Part 2: A mixture of 30 parts of water, 60 parts of 60 mesh iron dustand 5 parts of commercial muriatic acid is heated to about 90 andthereto 51 parts of the mixture of alkyl nitroben zene of Part 1 of thisexample are added slowly and incorporated in the reducing mixture byvigorous agitation. The whole reacting mass is heated and maintained atits refluxing temperature until reduction is complete. Completion of thereduction is ascertained by extracting a sample of the reaction masswith benzene, and pouring the benzene solution over a clean piece ofwhite filter paper. The reduction is finished it the spot on the paperafter the benzene has evaporated is free from yellow coloration. Thereduced mixture is neutralized with alkali, the liquid portion of thereduction mixture is removed from the solids, and allowed to settle. Theproduct separates as an oily layer above the aqueous mixture. It isremoved and after being washed with water several times it is .dried anddistilled. The fraction which distills from about 140 to about 225 at 7mm. of mercury pressure is collected as an amber-yellow oil, which isonly very slightly soluble in water. It is a mixture of C-alkylanilines.

Part 3: 25 parts of 26 per cent oleum are added very slowly to avigorously agitated and cooled charge of 25 parts of the mixture of C-alkyl anilines of Part 2 of this example. The temperature of the mixtureduring addition of the oleum is not allowed to exceed 40. Thereafter,the mixture is heated to about 70 and is held there until a sample isclearly soluble in water. Usually, the sulfonation is consideredsuflicient when 1 cc. of the sulfonated mixture is clearly soluble inabout 10 cc. of water at 25. The sulfonation mixture is poured intoabout 300 parts of water; the aqueous mixture is neutralizedwith'caustic soda or sodium carbonate and the solution is evaporated todryness. The dry product consists of a mixture of C-alkyl aniline sodiumsulfonates together with sodium sulfate. It is an excellent detergentand soap substitute.

Example 25.Part 1: In a reactor which is fitted with an agitator and areflux condenser, a vigorously agitated mixture or 200 parts of a crudechlorinated kerosene mixture of the type produced in the above Examples1 to 4, 100 parts benzoic acid and 35 parts anhydrous zinc chloride ismaintained at a temperature of about 135 until evolution of hydrogenchloride gas from the mixture practically ceases and thereafter for afurther period of about 2 to 3 hours. The total heating period is about6 hours. The agitated mixture is cooled, and at about 75 it is dilutedwith about 180 to abouteZQQ parts of denatured alcohol. The mixtureiscooled further to about 20 and is again diluted first with about 150parts of commercial ether, for the purpose of dissolving organicproducts, and second with a 10 per cent aqueous solution of hydrochloricacid for the purpose of dissolving inorganic bodies. The mixture isallowed to stand and to separate into two layers, the lower of whichconsists of an aqueous extract which is withdrawn and discarded. Theresidual upper layer, which is substantially a solution in the organicsolvent of the organic products in the condensed mass, is washed withcold or tepid water until it is reasonably free of acid and watersoluble products. It is then fractionally distilled in vacuo. Thefraction which distills between about 160 .and about 260 at 4 mm.pressure is separately collected. It is a viscous liquid which ispartially soluble in aqueous caustic soda solution.

Part 2: 25 parts of the distilled mixture of alkyl derivatives ofbenzoic acid of Part 1 of this example are rapidly agitated and mixedslowly with 18 parts of 100 per cent sulfuric acid while the temperatureof the agitated mixture is permitted to rise to about 50. Then 20 partsof 26 per cent oleum are added slowl and the temperature of the mixtureis maintained between about 60 and about 70. The mixture is agitated atthis temperature until the sulfonated products possess the desiredsolubility in aqueous solutions. (The sulfonation is usually consideredto be suflicient when about 1 cc. of the mixture is practicallycompletely soluble in about 10 cc. of water at about 25. This solubilityis usually attained at the end of about 1.5 hours of agitation followingthe addition of the oleum.)

The mixture is drowned with about 300 parts of water, the aqueousmixture is neutralized with caustic soda, and the neutral solution ofthe mixture of sodium sulfonates of alkyl derivatives of benzoic acid isevaporated to dryness. The dry mixture containing sodium sulfonates ofalkylderivatives of benzoic acid is a lightbrown to white friable solidwhich is readily soluble in water. Its aqueous solutions foam stronglyand have excellent wetting, penetrating and detersive powers.

Example 26.Part 1: A kerosene fraction of Pennsylvania petroleum boilingfrom 185 to 280 is fractionated and a fraction is collected.

between 91 at 13 mm. pressure and 109 at 12 mm. pressure. The collectedfraction boils from 200 to 235 at atmospheric pressure and per cent ofit boils between 212.5 and 231. Chlor'ine is passed into 340 parts ofthe resulting fraction maintained below 60, in the presence of light,until there is anincrease in weight of 88 parts.

Part 2: parts of the mixture produced in Part 1 of this example areadded with agitation, to a mixture of 80 parts of benzene and 4- partsof anhydrous aluminum chloride at ordinary temperature. The addition ismade as rapidly as possible. The mixture is agitated for one hour andthen allowed to separate. The resulting condensation product is decantedfrom the aluminum chloride sludge and washed with water, and the washedmaterial is stripped of unreacted materials by distilling. The portionboiling up to 118 at mm. and containing residual benzene is separatedfrom the remainder which comprises a mixture of alkyl benzene andresidual kerosene. It is similar in properties to the product of Example5, Part 1.

Part 3 '75 parts of the alkyl benzene product of Part 1 of this exampleis sulfonated with 1% times its weight of 26 per cent oleum. The oleumis added thereto at 10 to and the mixture is then agitated at roomtemperature for about 2- hours. The sulfonation mixture is diluted withfour times its weight of an ice-water mixture and neutralized withcaustic alkali (e. g., sodium hydroxide) to a pH of 7.0 to 8.0. Theneutral solution is evaporated to dryness on an atmospheric double drumdrier.

The mixtures of sulfonates as obtained in the above examples arelight-brown to white friable solids. They are very soluble in waterproducing solutions which foam readily. They do not precipitate calciumsalts from hard water, although a slight turbidity may be present. Theyhave detergent properties, and in general are excellent wetting anddispersing agents. While crude alkyl aromatic mixtures may be sulfonatedeither before or after the separation of residual aromatic compoundand/or aliphatic hydrocarbon from the mixture, the use of purified alkylaromatic compounds is preferred since they give sulfonation productshaving superior detergent properties.

It will be realized by those skilled in the art that changes may be madein the products, and in the processes of preparing and using them,hereinbefore described, without departing from the scope of theinvention.

Thus, the mixed alkyl aromatic sulfonates may be prepared in variousways from various aliphatic hydrocarbons having the characteristicsherein set out, and especially suitable fractions of petroleumdistillates. As above pointed out, the more important sources of rawmaterial for preparation of the alkyl aromatic compounds employed asintermediate products for the production of the sulfonated products arethe kerosene fractions derived from parafiinic petroleums; as farexample, those obtained from Pennsylvania, Michigan, Texas, and Oklahomapetroleums, those obtained from Pennsylvania petroleum and from Mt.Pleasant, Michigan, petroleum being especially preferred.

The chlorination of the petroleum hydrocarbon may be carried out by anywell known process. The approximate extent of chlorination may bedetermined by the increase in the weight of the hydrocarbon materialchlorinated or by the increase of the specific gravity of the mixture.

In general, the extent of chlorination of the petroleum hydrocarbon maybe regulated by a weight increase corresponding to a product containinga ratio of about one-fourth to 2.5 atoms of chlorine per molecule ofhydrocarbon, about 1.1 to 1.5 atoms being preferred, but it will beunderstood that other ratios may be used. Ordinarily, the greater theamount or extent of chlorination, the greater is the amount of highboiling residues obtained. In general, the monochloride boils about 15to 20 higher than the petroleum distillate from which it is derived. Ifdesired, the chlorinated products may be frictionally distilled so as toobtain a further selection and restriction of alkyl compounds having aselected content of chlorine atoms. Instead of chlorine, other halogensmay also be employed in effecting halogenation; e. g., bromine, etc.

Various chlorination temperatures may be employed, for exampletemperatures within the range 0 to 70, and preferably in theneighborhood of 50. The chlorination may be carried out with the aid ofchlorine carriers, catalysts or adjuvants; as for example, phosphorustrichloride, iodine, sunlight, etc. Chlorination in the presence oflight is preferred.

The condensation of the halogenated hydrocarbon with the aromaticcompound may be carried out with the aid of various condensing agents;as for example metals (such as, zinc or iron), metal halides (such as,anhydrous aluminum chloride,

anhydrous zinc chloride, anhydrous ferric chloride). The proportion ofmixed alkyl halides employed with respect to the aromatic compound inthe preparation of the alkylated aromatic compounds may be varied.Preferably the proportion of mixed halogenated hydrocarbons employedwith respect to the aromatic compound is such that only one alkylradical of the type represented by R above is contained in the resultingalkyl aromatic compounds. Thus, at least 1.2 mols of aromatic compoundper mol of mixed halogenated hydrocarbon is preferably employed in thecondensation. A molar ratio as low as 1 to 1 may be employed, but theyield of the resulting mixed alkyl aromatic compounds containing onelong alkyl group will be less.

The amount of condensing agent employed may vary over a wide range. Forexample, in using anhydrous metal chlorides as the condensing agent, insome cases as low as 1 per cent and in others about 5 to 20 per cent ormore by weight of anhydrous metal chloride, based upon the amount ofhalogenated petroleum hydrocarbon, may be employed. The condensationreaction may be carried out at various temperatures as is evident fromthe above examples.

Mixtures of aromatic compounds may be employed as reacting ingredients,if desired; as, for example, naturally occurring mixtures such ascommercial cresylic acid, or artificially prepared mixtures of two ormore of the aromatic compounds.

The alkyl aromatic compounds may be purified by fractional or steamdistillation, or by other suitable processes. Purification is notessential, but it is to be noted, by the employment of mixtures of alkylaromatic compounds which have been purified by fractional vacuumdistillation,

products having superior detergent properties are obtained as comparedto those produced when a relatively less pure mixture of alkyl aromaticcompounds is sulforfated.

The sulfonation of the mixture of alkyl aromatic compounds may becarried out with any suitable agent; as, for example, sulfuric acids ofvarious strengths (66 B., percent, 26 per cent oleum, 65 per cent oleum,etc.), chlorsulfonic acid, etc. As appears from the foregoing examples,the sulfonation may be carried out in the presence of inert solvents ordiluents, as for example, the halogenated aliphatic or aromatichydrocarbons (carbon tetrachloride, tetrachlor ethane, ethylenedichloride, dichlorbenzene, etc.) or sulfonation may be carried out intheir abscncc. When an inert solvent or diluent is used, it may beseparated mechanically or by evaporation from the alkaline aqueoussolution of the sulfonic acid salts of the alkyl aromatic compoundswhich results upon diluting the sulfonation mass with water and addingan alkali. If desired sulfonation assistants may be employed; as forexample the lower fatty acids and their anhydrides (e. g., acetic acid,acetic anhydride, etc.) or the alkali metal sulfates (e. g., sodium orpotassium sulfate, etc.).

The temperature at which the sulfonation is carried out may vary withinwide limits. For example, temperatures as low as about and as high asabout 140 may be employed. In general the more vigorous the sulfonationagent the lower is the preferred temperature. Preferred sulfonationtemperatures lie between about 15 and about 90. Ordinarily thecompletion of the sulfonation is carried out at a. temperature of about35 to about 80". In using sulfuric acid monohydrates as the sulfonatingagent, a temperature of about 30 to 70 is referred.

The ratio of sulfonating agent employed with respect to the mixture ofalkyl aromatic compounds also may be varied. Thus, for completesulfonation, the sulfonating agent in terms of 100 per cent sulfuricacid may range from 0.3 to times or more the weight of the alkylaromatic compounds to be sulfonated. The extent to which the sulfonationis carried out may vary with the individual material being sulfonated,the duration or time of sulfonation, and the use to be made of thesulfonated product. In some cases, a degree of sulfonation whichcorresponds with a product having maximum detergent properties is notcompletely soluble in water to form a clear solution and/or may causesome precipitation of lime salts. On the other hand, a product whichcauses no precipitation of lime salts may not have maximum obtainabledetergent properties because of excessive sulfonation. Furthermore, insome cases the degree of sulfonation may not be the same for products tobe used as detergents in soft water, in hard water and in alkalinesolutions. (As a standard of comparison,

an aqueous solution of calcium chloride equiva- I lent to 0.224 gramscalcium oxide per liter of solution is employed as a standard hardwater.) For use of the products in accordance with the presentinvention, a degree of sulfonation corresponding with maximum detergentaction (approximately monosulfonation) is preferred.

The sulfonated products-may be employed in the form of their freesulfonic acids or in the form of salts. They are preferably employed inaccordance with the present invention in the form of salts of the alkalimetals. The salts may-be obtained in any suitable manner; for example,by reacting the sulfonated product with a metal oxide or hydroxide,ammonia or an organic base, or of a suitable salt of one of these, in anamount adapted to form a neutral product. Among the bases, oxides andsalts which may be combined with the sulfonated products to producesalts useful as detergents in accordance with the present invention,are, for example, sodium, potassium and ammonium hydroxides; sodium,potassium and ammonium carbonates and bicarbonates; ammonia; magnesiumoxide; ethylamine; pyridine; triethanolamine; propanolamines;butanolamines; diamino propanol; ethylene diamine; triethylenetetramine; aniline; o-toluidine; etc.

The reaction mixtures resulting from the sulfonation of the mixed alkylaromatic compounds may also be directly employed for the formation ofmixed products, as for example, mixtures of salts of the alkyl aromaticsulfonic acids and other acids present in said reaction mixtures, whichmixtures of salts are also useful as detergents i accordance with thepresent invention. Thus', the sulfonation reaction mixture resultingfrom the treatment of the mixed alkyl aromatic compounds with an amountof sulfonating agent in excess of that theoretically required to effectthe desired degree of sulfonation may be treated with a suitableinorganic or organic base or basic salt (as for example, one of thosementioned) and the resulting mixture of the salt of the sulfonated alkylaromatic compounds and the inorganic salt (as for example, sodiumsulfate) may be jointly isolated from the reaction mixture and employedas such. If it is desired to produce salts of the sulfonated alkylaromatic compounds in a form substantially free from inorganic salts(for example, inorganic sulfates) this may be accomplished by takingadvantage of their greater solubility than the inorganic salts inalcohol and other organic solvents, or by using an amount ofchlorsulfonic acid such that no excess, or only a relatively smallexcess, of same is present in the final sulfonation mass or mixture.

The sulfonated products in the form of metallic salts or salts ofinorganic bases are usually yellowish to white, friable solids; and inthe form of salts of organic bases vary from viscous oils to semi-solidsto solids. In general, the salts are readily soluble in water and inneutral, acid or alkaline aqueous solutions to form solutions which arecolorless or faintly colored brown or yellow, which are of a soapynature, and foam readily. Certain of the salts, such as the impure saltsof organic polyamines, are oils which generally are insoluble in waterbut soluble in organic solvents (as for example, alcohol, benzene.gasoline, etc.), in which they exert detergent action, and in aqueoussolutions of alkalies (preiumably by conversion to the salts of thealka- The sulfonated products may be dried in any suitable manner; theyare preferably dried on atmospheric or vacuum drum driers or in spraydriers. Preferably the sulfonates derived from organic bases are driedunder vacuum conditions.

The said sulfonation products may be used in powder or in paste form, orin solution, as wetting, dispersing or emulsifying agents instead of theusual soaps, and/or for scouring, cleaning, washing, toilet and otherpurposes for which ordinary soaps have heretofore been employed,

with or without the presence of, or admixture with, abrasive material,e. g., whiting, pumice, etc. They also may be employed in conjunction,orin admixture, with an ordinary soap (a higher fatty acid salt), asdisclosed and claimed in my copending application Serial No. 403,235,filed July 19, 1941; since it has been found that the sulfonationproducts of the present invention, when jointly present with an ordinarysoap, prevent or hinder formation of objectionable precipitates whichare otherwise produced by soap when used in hard water or in acid orsalt baths. The sulfonation products of the present invention have thefurther advantage of being, in general, better wetting agents, of beingmore readily soluble in water and various organic solvents than theusual soaps, and of leaving goods washed therewith with a soft feel.Inasmuch as water solutions of said sulfonation products in the form oftheir alkali metal salts are neutral in reaction, they may be safelyused for the washing of delicate silks and other fine fabrics, as wellas I or personal toilet purposes.

In addition to their usefulness as detergents as herein disclosed, themixed alkyl aromatic sulfonates may be employed either in the form ofthe free acids or their metal, ammonium or organic ammonium salts aswetting, impregnating, dispersing, assisting, penetrating, insecticidaland fungicidal agents.

It is to be noted that mixtures of two or more of the sulfonatedproducts hereinbefore referred to may be employed. Furthermore, any ofthe said sulfonated products or their mixtures may be employed inconnection with other hydrotropic substances; dispersing, emulsifyingand/or penetrating agents; aliphatic or aromatic sulfonic acids; acidalkyl esters of sulfuric acid; sulfonation products of petroleum oil;alkyl aryl sulfonates free from a nuclear hydroxyl group; and/or theirderivatives.

I claim:

1. A mixture of alkyl derivatives of an aromatic sulfonate of which thealkyl groups correspond with the hydrocarbons of an aliphatichydrocarbon mixture at least 80 per cent of which boils between 210 and320 C. and over a maximum range of 55 C., and obtainable by a processcomprising halogenation of the aliphatic hydrocarbon mixture to formmixed alkyl halides, and condensation of resulting mixed alkyl halideswith an aromatic compound followed by sulfonation.

2. A mixture of alkyl derivatives of an aromatic sulfonate of which thealkyl groups correspond with the aliphatic hydrocarbons of a petroleumdistillate of which at least 80 per cent boils between 210 and 320 C.and over a maximum range of 55 C., and obtainable by a processcomprising chlorinating said petroleum distillate, to form mixed alkylchlorides, and condensing resulting mixed alkyl chlorides with anaromatic compound followed by sulfonation.

3. A mixture of alkyl derivatives of an aromatic sulfonate of thebenzene series of which the alkyl groups correspond with the aliphatichydrocarbons of a petroleum distillate of which at least 80 per centboils between 210 and 320 and over a maximum range of 55 C., andobtainable by a process comprising chlorinating said petroleumdistillate, to form mixed alkyl chlorides, and condensing resultingmixed alkyl chlorides with an aromatic compound of the benzene seriesfollowed by sulfonation.

4. A mixture of alkyl derivatives of an aromatic sulfonate the alkylgroups of which contain between 12 and 19 carbon atoms and are derivedfrom mixed alkyl chlorides resulting from chlorination of a petroleumdistillate of which at least 80 per cent boils between 210 and 320 C.and over a maximum range of 55 C.

5. A mixture of monoalkyl derivatives of an aromatic sulfonate of whichthe alkyl groups are derived from a halogenated Pennsylvania petroleumdistillate at least 80 per cent of which petroleum distillate boilsbetween 210 and 320 C. and over a maximum range of 30 C.

6. A mixture of monoalkyl derivatives of an aromatic sulfonate of whichthe alkyl groups are derived from a mixture of alkyl chlorides resultingfrom chlorination of a mixture of aliphatic hydrocarbons of the type ofPennsylvania petroleum distillate boiling between 210 and 290 C.

of which at least per cent boils over a maximum range of 55 C.

7. A mixture of monoalkyl derivatives of a phenyl sulfonate of which thealkyl groups are derived from a petroleum distillate of which at least80 per cent boils between 210 and 320 C. and over a maximum range of 55C.

8. A mixture of monoalkyl derivatives of a phenyl sulfonate of which thealkyl groups contain 12 to 19 carbon atoms and are derived from achlorinated Pennsylvania petroleum distillate, at least 80 per cent ofwhich petroleum distillate boils between 210 and 320 C. and over amaximum range of 30 C.

9. A method of making a sulfonated product, which comprises halogenatingan aliphatic hydrocarbon mixture at least 80 per cent of which boilsbetween 210 and 320 C. and over a maximum range of 55 C., to form amixture of alkyl halides, condensing resulting mixed alkyl halides withan aromatic compound, and then sulfonating.

10. A method of making a sulfonated product, which compriseshalogenating a petroleum distillate at least 80 per cent of which boilsbetween 210 and 320 C. and over a maximum range of 55 C., to form amixture of alkyl halides, condensing resulting mixed alkyl halides withan aromatic compound to produce a mixture of alkyl derivatives of saidaromatic compound, and sulfonating a mixture of said alkyl derivatives.

11. A method of making a sulfonated product, which compriseshalogenating a petroleum distillate of which 80 per cent consists ofaliphatic hydrocarbons containing between 12 and 19 carbon atoms permolecule and boiling between 210 and 320 C. and over a maximum range of55 C.. to produce a mixture of alkyl halides, condensing resulting mixedalkyl halides with an aromatic compound to produce a mixture of alkylderivatives of said aromatic compound, and sulfonating a mixture of.said alkyl derivatives.

12. A method of making a sulfonated product, which comprises reactingchlorine with a petroleum distillate of which 80 per cent consists ofaliphatic hydrocarbons containing between 12 and 19 carbon atoms permolecule and boiling between 210 and 320 C. and over a maximum range of55 C., to produce a mixture of alkyl chlorides, condensing resultingmixed alkyl chlorides with an aromatic compound to produce a mixture ofalkyl derivatives of said aromatic compound, and sulfonating a mixtureof said alkyl derivatives.

13. A method of making a sulfonated' product, which compriseschlorinating a mixture of aliphatic hydrocarbons of the type ofPennsylvania petroleum distillate at least 80 per cent of which boilsbetween 210 and 320 C. and over a maximum range of 55 C., carrying outthe chlorination under conditions resulting in a product containing aratio of about 1.1 to 15 atoms of chlo rine per molecule of hydrocarbon,condensing the resulting mixture of alkyl chlorides with an aromaticcompound of the benzene series with the aid of a metal halide condensingagent, and sulfonating a resulting mixture of alkyl derivatives of thearomatic compound.

14. A method of making a sulfonated product, which compriseschlorinating a, Pennsylvania petroleum distillate boiling between 210and 290 C. of which at least 80 per cent boils over a maximum range of55 C., carrying out the chlorination under conditions resulting mainlyin the formation of alkyl monochlorides, condensing the resultingmixture of alkyl monochlorides with an tives of the aromatic compound.

15. A method of making a sulfonated product, which compriseschlorinating a petroleum distillate of the type of Pennsylvaniapetroleum distillate of which at least 80 per cent boils between 210 and265 C. to produce a mixture of alkyl chlorides, condensing resultingmixed alkyl chlorides with an aromatic hydrocarbon of the benzene seriesto producea mixture of alkyl derivatives of said aromatic hydrocarbon,and sulfonating a mixture of said alkyl derivatives.

16. A method of making a sulfonate'd product, which compriseschlorinating a petroleum distillate of the type of Pennsylvaniapetroleum distillate of which at least 80 per cent boils between 210 and265 C. to produce a mixture of alkyl chlorides, condensing resultingmixed alkyl chlorides with benzene to produce a mixture of alkylderivatives of benzene, and sulfonating a mixture of said alkylderivatives.

17. A mixture of alkyl derivatives of an arcmatic sulfonate of which thealkyl groups are.

derived from an aliphatic hydrocarbon mixture of which at least 80 percent boils between 210 and 265 C. a

18. A mixture of monoalkyl derivatives of an aromatic monosulfonate ofthe benzene series of which the alkyl groups are derived from apetroleum hydrocarbon mixture of which at least 80 per cent boilsbetween 210 and 265 C., and obtained by a process comprisingchlorinating said petroleum hydrocarbonmixture to form mixed alkylchlorides, condensing resulting mixed alkyl chlorides with an aromatichydrocarbon of the benzene series to produce a mixture of alkylderivatives of said aromatic hydrocarbon, and sulfonating a mixture ofsaid alkyl derivatives.

19. A mixture of monoalkyl derivatives of phenyl monosulfonate of whichthe alkyl groups are derived from a paraflinic petroleum kerosene 80 percent of which kerosene boils within the range 210 to 265 C.

20. A method of making a sulfonated product, which compriseschlorinating a kerosene derived from a paraflinic petroleum at least 80per cent of which kerosene boils within the range 210 to 265 C.,condensing mixed alkyl chlorides resulting from the chlorination with anaromatic compound to produce a mixture of alkyl derivatives of saidaromatic compound, and sulfonating a mixture of said alkyl derivatives.

- 21. A-method of making a sulionated product, which compriseschlorinating a mixture of aliphatic hydrocarbons of the type oi.Pennsylvania petroleum distillate at least 80 per cent of which boilsbetween 210 and 320 C. and over a maximum range of C., carrying out thechlorination under conditions resulting in a product containing a ratioof about 1.1 to 1.5 atoms of chlorine per molecule of hydrocarbon,condensing the resulting mixture of alkyl chlorides with an aromaticcompound of the benzene series with the aid of aluminum chloride as acondensing agent, the amount of aromatic compound of the benzene seriesemployed in the condensation being at least 1.25 mols per mol of themixture of alkyl chlorides, and sulfonating a resulting mixture of alkylderivatives of the aromatic compound.

22. A mixture of monoalkyl derivatives of an alkoxy-aromatic sulfonateof which the alkyl groups are derived from a petroleum distillate ofwhich at least per cent boils between 210 and 320 C. and over a maximumrange of 55 C., the alkoxy group of the. alkoxy-aromatic sulfonatecontaining 1 to 8 carbon atoms.

23. A mixture of monoalkyl derivatives of a phenetol sulfonate of whichthe alkyl groups are derived from a petroleum distillate of which atleast 80 per cent boils between 210 and 320 C. and over a maximum rangeof 55 C.

24. A mixture of monoalkyl derivatives of a phenetol sulfonate of whichthe alkyl groups are derived from a paraflinic petroleum kerosene 80 percent of which kerosene boils within the range 210 to 265 C.

25. A mixture of monoalkyl derivatives of a hydroxy-aromatic sulfonateof which the alkyl groups are derived from a petroleum distillate ofwhich at least 80 per cent boils between 210 and 320 C. and over amaximum range of 55 C.

26. A mixture of monoalkyl derivatives of a phenol monosulfonate ofwhich the alkyl groups are derived from a petroleum distillate of whichat least 80 per cent boils between 2'"? and 320 C. and over a maximumrange of 55' 2.

27. A mixture of monoalkyl derivatives of a phenol monosulfonate ofwhich the alkyl groups are derived from a paraflinic petroleum kerosene80 per cent of which kerosene boils within the range 235 to 320 C. andover a maximum range of 55 C.

LAWRENCE H. FLE'IT.

